全文获取类型
收费全文 | 4130篇 |
免费 | 169篇 |
国内免费 | 12篇 |
专业分类
化学 | 2616篇 |
晶体学 | 26篇 |
力学 | 93篇 |
综合类 | 1篇 |
数学 | 543篇 |
物理学 | 1032篇 |
出版年
2023年 | 41篇 |
2022年 | 46篇 |
2021年 | 45篇 |
2020年 | 69篇 |
2019年 | 57篇 |
2018年 | 45篇 |
2017年 | 32篇 |
2016年 | 112篇 |
2015年 | 121篇 |
2014年 | 111篇 |
2013年 | 174篇 |
2012年 | 184篇 |
2011年 | 198篇 |
2010年 | 135篇 |
2009年 | 131篇 |
2008年 | 198篇 |
2007年 | 190篇 |
2006年 | 178篇 |
2005年 | 193篇 |
2004年 | 147篇 |
2003年 | 128篇 |
2002年 | 104篇 |
2001年 | 83篇 |
2000年 | 66篇 |
1999年 | 58篇 |
1998年 | 34篇 |
1997年 | 43篇 |
1996年 | 47篇 |
1995年 | 50篇 |
1994年 | 59篇 |
1993年 | 71篇 |
1992年 | 71篇 |
1991年 | 49篇 |
1990年 | 45篇 |
1989年 | 42篇 |
1988年 | 37篇 |
1987年 | 43篇 |
1986年 | 45篇 |
1985年 | 41篇 |
1984年 | 52篇 |
1983年 | 39篇 |
1982年 | 41篇 |
1981年 | 47篇 |
1980年 | 48篇 |
1979年 | 40篇 |
1978年 | 38篇 |
1977年 | 46篇 |
1976年 | 47篇 |
1974年 | 26篇 |
1973年 | 36篇 |
排序方式: 共有4311条查询结果,搜索用时 31 毫秒
51.
Progressive reaction networks as frequently arise in chemistry are naturally identifiable as "partially ordered sets" (or posets). Here the direction of the reaction identifies the partial ordering of the set of molecular species. The possibility that different properties are similarly ordered is a further natural consideration and is here investigated for a suite of over 30 properties for (methyl and chloro) substituted benzenes. Such a posetic correlation is favorably demonstrated for these substituted benzenes, and it is illustrated how suitable properties may be simply predicted in an interpolative parameter-free (albeit not model-free) fashion through the use of the reaction poset. Some numerical model-quality indicators are identified, and the simple approach is deemed quite reasonable. 相似文献
52.
Sven Rau 《Journal of organometallic chemistry》2004,689(22):3582-3592
The binuclear complex [(acac)Pd(oxam)Pd(acac)] 1 (oxam: tetraphenyl oxalic amidinate) has been prepared from H2oxam and Pd(acac)2 in excellent yield. The complex was characterized by elemental analyses, mass spectroscopy, 1H NMR, 13C NMR spectroscopy and in the solid state by X-ray single crystal diffraction analyses. 1 consists of a bimetallic centrosymmetric unit in which the planar oxam ligand acts in a bis-chelating fashion. Each palladium center is in a planar environment.The complex 1 acts as highly selective pre-catalyst in the copper-free Sonogashira reaction between 4-bromoacetophenone and phenylacetylene. Its long-time catalytic activity is higher than that of the related binuclear complex 2 (oxam: tetra-p-tolyl oxalic amidinate) or that of the trinuclear compound [(acac)Pd(oxam)Zn(oxam)Pd(acac)] (3), the solid-state structure of which was also determined by an X-ray structural analysis of single crystals. In addition, 2 is an active and extremely selective pre-catalyst for the Negishi reaction between 3,5,6,8-tetrabromophenanthroline and R-CC-ZnCl (R: Ph, (iprop)3Si) to form tetra-alkyne-substituted derivatives. 相似文献
53.
Pre-resonance Raman spectra have been obtained for TCNQ and LiTCNQ in acetonitrile solution using an Ar+—Kr+ laser and a tunable rhodamine 6G dye laser. Using the theory of Albrecht and Hutley, we have calculated frequency factors for the intensity variations for several symmetric vibrational modes of each molecule. The observed spectra for TCNQ and LiTCNQ with violet, blue, and green excitation give evidence for B-type resonance enhancement due to vibronic mixing between at least two violet and ultraviolet transitions. The Raman spectra for LiTCNQ with yellow, orange, and red excitation show A-type enhancement due to a single electronic excitation in the near infrared. 相似文献
54.
The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 . 相似文献
55.
A simple semiconductor gas sensor (TGS 812) is used for the on-line measurement and control of indole during the production of l-tryptophan from indole and l-serine with immobilized E. coli cells. Indole is estimated in the reactor gas space. In combination with an automatic indole supply system, a feed-batch process became possible. The indole concentration was monitored and kept within the optimal range (300–600 mg l?1). A simple gas-sensing electrode dipped in the reaction medium provides direct measurement of organic solvents and gases in the liquid. Such a system is suitable for on-line determination of ethanol (10–70 g l?1) during continuous production of ethanol with immobilized yeast cells. 相似文献
56.
The 13C NMR data of some mono- and disubstituted adamantanes, homoadamantenes and homonoradamantenes are presented. A model of dependencies of the γanti substituent induced shifts on torsion angles and internuclear distances between substituents and the γ carbons is proposed. Furthermore, it is shown that for the α substituent induced shifts strain within the molecular frameworks of these compounds plays no significant part. 相似文献
57.
The systems AeAl(2-x)Mgx (Ae = Ca, Sr, Ba) display electron concentration induced Laves phase structural changes. However, the complete sequence MgCu2 --> MgNi2 --> MgZn2 with increasing x (decreasing electron count) is only observed for Ae = Ca. Compounds SrAl(2-x)Mgx (0 < x < or = 2) and BaAl(2-x)Mgx (x = 0.85 and 2.0) were synthesized and structurally characterized by X-ray diffraction experiments. For the Sr system the structural sequence CeCu2 --> MgNi2 --> MgZn2 occurs with increasing Mg content x. Thus, larger Sr does not allow the realization of the MgCu2 structure at low x. For Ae = Ba a binary compound BaAl2 does not exist, but more Ba-rich Ba7Al13 forms. The reinvestigation of the crystal structure of Ba7Al13 by selected area and convergent beam electron diffraction in a transmission electron microscope revealed a superstructure, which subsequently could be refined from single X-ray diffraction data. The formula unit of the superstructure is Ba21Al40 (space group P31m, Z = 1, a = 10.568(1) angstroms, c = 17.205(6) angstroms). In Ba21Al40 a size match problem between Ba and Al present in Ba7Al13 is resolved. The structure of Ba7Al13 (Ba21Al40) can be considered as a Ba excess variant of the hexagonal MgNi2 Laves phase type structure. An incommensurately modulated variant of the MgNi2 structure is obtained for phases BaAl(2-x)Mgx with x = 0.8-1. At even higher Mg concentrations a structural change to the proper MgZn2 type structure takes place. 相似文献
58.
Hausner SH Striley CA Krause-Bauer JA Zimmer H 《The Journal of organic chemistry》2005,70(15):5804-5817
Dibenzotetraaza (DBTA) crown ethers possess two o-phenylenediamine moieties. They are homologues of dibenzo crown ether phase-transfer catalysts and were prepared from the condensation of benzimidazoles with oligo(ethyleneglycol) dichlorides and oligo(ethyleneglycol) ditosylates. Compounds with ring sizes ranging from 18-crown-6 to 42-crown-14 were prepared. In addition, various altered benzimidizoles were used to produce DBTA crown ethers with modified substituents and ether bridges, as well as benzimidazolidine crown ethers. The synthetic approach presented here proved to be a convenient route to a new family of crown ethers with overall yields of up to 48% based on the benzimidazole. Yields for the ring-closing step were generally high, ranging from 51% to 94%, without the need for high-dilution conditions. Reaction of the DBTA crown ethers with alkyl and benzyl halides was found to be a facile way to obtain the corresponding tetra(N-organyl) compounds. Picrate extraction studies were carried out to determine phase-transfer catalytic capabilities. Extraction efficiencies for alkali-metal ions were lower than those for dibenzo-18-crown-6. Efficiencies were higher for other metal ions, with some selectivity for Pb(2+). Tetra(N-methyl) DBTA-18-crown-6 generally exhibited higher extraction efficiencies than its N-H analogue, but the selectivity was lower. 相似文献
59.
60.
Phenyl vinyl sulfonate reacts with various alkyl furan derivatives under mild conditions to produce excellent yields of the corresponding cycloadducts. 相似文献